ES2742752T3 - Process for the production of highly polymerized aromatic polycarbonate resin - Google Patents

Abstract

Process for producing a highly polymerized aromatic polycarbonate resin comprising a highly polymerizing process, in which the aromatic polycarbonate is bonded with an aliphatic diol compound having a boiling point of 240°C or higher through a transesterification reaction in the presence of a reduced pressure transesterification catalyst to increase molecular weight, wherein the aliphatic diol compound is selected from the group consisting of 4,4'-bis(2-hydroxyethoxy)biphenyl, 9,9'-bis[4 -(2-hydroxyethoxy)phenyl]fluorene, fluorene glycol and fluorene diethanol, and wherein the highly polymerized aromatic polycarbonate resin has a weight average molecular weight (MW) of 30,000-100,000.

Description

DESCRIPTION

Process for the production of highly polymerized aromatic polycarbonate resin

Technical field

The present invention relates to a method for highly polymerizing an aromatic polycarbonate resin. More precisely, the present invention relates to a process for producing a polycarbonate resin with high quality and a high degree of polymerization in which the PM is approximately 30,000-100,000, by extending the chain joining the terminal groups with busy ends of aromatic polycarbonate with an aliphatic diol compound. The present invention further relates to a highly polymerized aromatic polycarbonate resin obtainable by the process and a molded product, to a sheet or film product obtainable from the highly polymerized aromatic polycarbonate resin.

Prior art

Since polycarbonate is excellent in heat resistance, impact resistance and transparency, it has been widely used in many fields in recent years. Various studies have been carried out with procedures for the production of polycarbonate. Among them, the polycarbonate derived from aromatic dihydroxy compounds such as 2,2-bis (4-hydroxyphenyl) propane, hereinafter "bisphenol A", is industrialized by both interfacial polymerization and melt polymerization processes .

According to interfacial polymerization, polycarbonate is produced from bisphenol A and phosgene, but toxic phosgene has to be used. In addition, it remains a problem such as corrosion of equipment caused by by-products such as hydrogen chloride and sodium chloride, and chlorine-containing compounds such as methylene chloride used in large quantities as a solvent, and difficulties in removing impurities. such as sodium chloride or residual methylene chloride that could influence the properties of the polymer. Meanwhile, as a method of producing polycarbonate from an aromatic dihydroxy compound and diarylcarbonates, a molten state polymerization method has long been known, in which, for example, bisphenol A and diphenyl carbonate are polymerized through a transesterification reaction under melting conditions such as elimination of aromatic monohydroxyl compounds byproducts. Unlike the interfacial polymerization method, the molten state polymerization method has advantages such as not using solvents. However, it has an essential problem as follows: as polymerization occurs, the viscosity of the polymer in the system increases dramatically, making it difficult to efficiently remove aromatic monohydroxyl compounds by-products outside the system, which could cause The reaction rate decreases extremely, making it difficult to increase the degree of polymerization.

To solve the above problem, various attempts have been studied to extract the aromatic monohydroxyl compounds from the polymer under conditions of high viscosity. For example, patent document 1 (Japanese patent Kokoku No. S50-19600) discloses a polymerization container of the helix type having a vent. In addition, patent document 2 (Japanese patent Kokai No. H02-153923) discloses a method using a thin film evaporator in combination with a horizontal polymerization device.

Patent document 3 (US Patent No. 5,521,275) discloses a method for redistributing the molecular weight of an aromatic polycarbonate in the presence of a catalyst using an extruder having a polymer seal and reduced pressure ventilation.

However, the methods disclosed in the previous documents would not be able to sufficiently increase the molecular weight of polycarbonate. The above methods for increasing the molecular weight using catalyst in large quantity or using strict conditions such as applying high shear could cause problems that would have a significant influence on the polymer such as deterioration of the tone or the progress of a crosslinking reaction.

It is known that the degree of polycarbonate polymerization can be increased by adding a polymerization accelerator in the molten polymerization reaction system. Increasing the molecular weight in a short reaction residence time and a low reaction temperature makes it possible to increase the production volumes of polycarbonate, which would facilitate designing simple and economical reaction vessels.

Patent document 4 (European Patent No. 0 595 608) discloses a method for reacting many diaryl carbonates at the time of redistribution that, however, would not produce a significant increase in molecular weight. Patent document 5 (US Patent No. 5,696,222) discloses a method for producing a highly polymerized polycarbonate by adding a certain type of polymerization accelerator such as aryl ester compounds of carbonic acid and dicarboxylic acid including bis ( 2-methoxyphenyl), bis (2-ethoxyphenyl) carbonate, bis (2-chlorophenyl) carbonate, bis (2-methoxyphenyl) terephthalate and bis (2-methoxyphenyl) adipate.

Patent document 6 (Japanese Patent No. 4,112,979) discloses a method of reacting many salicylic carbonates with an aromatic polycarbonate to increase their molecular weight.

Patent document 7 (Japanese unexamined patent application publication (PCT application translation) No. 2008-514754) discloses a method of introducing a bis-salicylic polycarbonate and carbonate oligomer or the like into an extruder to increase the molecular weight.

Patent document 8 (Japanese Patent No. 4286914) discloses a method of increasing the amount of terminal hydroxyl groups by means of an active hydrogen compound such as a dihydroxy compound, and subsequently carrying out a coupling reaction of the aromatic polycarbonate which it has the increased amount of terminal hydroxyl groups using an ester derivative of salicylic acid.

However, the method disclosed in the previous document that requires the amount of polycarbonate terminal hydroxyl groups is complicated in the processes because it requires both a reaction process with an active hydrogen compound and a reaction procedure with an acid ester derivative salicylic. In addition, according to the method, polycarbonate having many terminal hydroxyl groups is of low thermal stability and is at risk of deterioration of physical properties. As shown in non-patent documents 1-2, the increase in the amount of hydroxyl groups by means of active hydrogen compounds could induce a partial chain decoupling reaction accompanied by a broadening of the molecular weight distribution. In addition, a relatively large amount of catalyst is required to obtain a sufficiently high reaction rate, which could result in deterioration of physical properties at the time of the formation procedures.

Patent document 9 (Japanese patent Kokoku No. H06-94501) discloses a process for producing a high molecular weight polycarbonate by introducing 1,4-cyclohexanediol. According to the method disclosed therein, however, 1,4-cyclohexanediol is introduced together with an aromatic dihydroxyl compound into the polycondensation reaction system from the beginning and therefore, 1,4-cyclohexanediol would be consumed first by the polycarbonate bond formation reaction to form an oligomer, and then the aromatic dihydroxy compound would be reacted to participate in the high polymerization reaction. For this reason, it has a defect such that the reaction time would become relatively long, which could cause deterioration of the appearance characteristics such as color or tone.

Patent document 10 (Japanese patent Kokai No. 2009-102536) discloses a process for producing specific polycarbonate copolymerizing aliphatic diol and etherdiol. However, since the polycarbonate disclosed therein has an isosorbide skeleton as the main structure, the excellent impact resistance required for aromatic polycarbonates would not be shown.

In addition, patent document 11 (US 5,294,729) describes a process for preparing a block oligocarbonate, in which an aromatic polycarbonate could be reacted with an aliphatic polyol, such as a polyester polyol or a polyether polyol.

Patent document 12 (US 6,300,459) refers to a process, in which an aromatic polycarbonate and an active hydrogen compound are subjected to the transesterification reaction in the presence of a reduced pressure transesterification catalyst followed by the reaction with an ester derivative of salicylic acid. The active hydrogen compound could be diol such as bisphenol A or neopentyl glycol.

In patent document 13 (JP 33 01453 B2), a process for obtaining a polycarbonate is described, in which a dihydroxy compound and a carbonic diester are subjected to transesterification under the condition that a reaction system is added to the reaction system. diol having hydroxyl groups having a higher basicity than those of the hydroxyl groups of the dihydroxyl compound after the conversion of the transesterification exceeds 70%. Examples of the diol compound are diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-decanediol and 2,2-bis (4-hydroxycyclohexyl) propane.

As mentioned earlier, conventional methods for producing highly polymerized aromatic polycarbonate present many problems, and there are still requests to develop an improved production method that allows the increase in molecular weight of the aromatic polycarbonate resin satisfactorily while maintaining good quality. which originally has polycarbonate.

Prior art documents

[Patent documents]

Patent document 1: Japanese patent Kokoku No. S50-19600

Patent document 2: Japanese patent Kokai No. H02-153923

Patent document 3: U.S. Patent No. 5,521,275

Patent document 4: European Patent No. 0595608

Patent document 5: U.S. Patent No. 5,696,222

Patent document 6: Japanese patent No. 4112979

Patent document 7: Japanese patent application publication not examined (translation of PCT application) No. 2008-514754

Patent document 8: Japanese patent No. 4286914

Patent document 9: Japanese patent Kokoku No. H06-94501

Patent document 10: Japanese patent Kokai No. 2009-102536

Patent document 11: U.S. Patent No. 5,294,729

Patent document 12: U.S. Patent No. 6,300,459

Patent document 13: Japanese Patent No. 3301453

[Non-patent documents]

Non-patent document 1: "Polycarbonate Handbook", published by Nikkan Kogyo Shimbun Ltd., p. 344 Non-patent document 2: “Polycarbonate Resin” published by Nikkan Kogyo Shimbun Ltd. “Plastic Material” p.

144

Disclosure of the invention

Problems to be solved by the invention

The problem to be solved by the present invention is to provide an improved method for producing a highly polymerized aromatic polycarbonate resin that allows the increase in molecular weight of the aromatic polycarbonate resin satisfactorily while maintaining good quality. A further problem is the provision of a highly polymerized aromatic polycarbonate resin obtainable by the process and a molded product obtainable from the resin.

Means to solve the problems

As a result of intensive studies to solve the above problems, the present inventors have found that a highly polymerized aromatic polycarbonate resin can be produced by a simple procedure by carrying out a transesterification reaction between an aromatic polycarbonate resin with busy ends and a compound of specific aliphatic diol in the presence of a transesterification catalyst under reduced pressure, thus completing the present invention.

That is, the present invention relates to a process for producing as follows:

[1] A process for producing a highly polymerized aromatic polycarbonate resin comprising a highly polymerizing process, wherein aromatic polycarbonate is bonded with an aliphatic diol compound having a boiling point of 240 ° C or higher through a transesterification reaction in the presence of a transesterification catalyst under reduced pressure to increase molecular weight,

wherein the aliphatic diol compound is selected from the group consisting of 4,4'-bis (2-hydroxyethoxy) biphenyl, 9,9'-bis [4- (2-hydroxyethoxy) phenyl] fluorene, fluorenoglycol and fluorenedioethanol, Y

wherein the highly polymerized aromatic polycarbonate resin has a weight average molecular weight (MW) of 30,000-100,000.

[2] The process according to [1], wherein said aliphatic diol compound is added in the amount of 0.01 to 1.0 moles per mole of the total amount of the end groups of the aromatic polycarbonate before said reaction of transesterification

[3] The process according to [1] or [2], in which the aromatic polycarbonate prior to said transesterification reaction in the highly polymerizing process has at least partially occupied ends.

[4] The process according to [3], wherein the aromatic polycarbonate before said transesterification reaction is a prepolymer with terminally occupied ends obtained by reacting an aromatic dihydroxy compound with diester carbonate.

[5] The process according to [3] or [4], wherein the aromatic polycarbonate prior to said transesterification reaction in the highly polymerizing process has the concentration of terminal hydroxyl groups of 1,500 ppm or less.

[6] The process according to any one of [1] to [5], in which the weight average molecular weight (MW) of the highly polymerized aromatic polycarbonate resin after the transesterification reaction in the highly polymerizing process is increased at 5,000 or more compared to that of aromatic polycarbonate before the transesterification reaction.

[7] The process according to any one of [1] to [6], wherein the weight average molecular weight (MW) of the aromatic polycarbonate before the transesterification reaction in the highly polymerizing process is 5,000 to 60,000.

[8] The process according to any one of [1] to [7], wherein the transesterification reaction in the highly polymerizing process is carried out at a temperature ranging from 240 ° C to 320 ° C under reduced pressure.

[9] The process according to any one of [1] to [8], in which the transesterification reaction in the highly polymerizing process is carried out at a reduced pressure ranging from 13kPaA (100 torr) to 0.01 kPaA (0.01 torr).

[10] The process according to any one of [1] to [9], which comprises a prepolymer production process in which a prepolymer is produced with ends occupied in a terminal manner by reacting an aromatic dihydroxy compound with diester carbonate, and a highly polymerizing process in which said prepolymer with terminally occupied ends binds with an aliphatic diol compound having a boiling point of 240 ° C or higher through a transesterification reaction in the presence of a transesterification catalyst under reduced pressure to increase molecular weight.

[11] A highly polymerized aromatic polycarbonate resin obtained by the process according to any one of [1] to [10].

[12] A molded product, sheet or film product obtainable from the highly polymerized aromatic polycarbonate resin according to claim 11 by injection molding, blow molding, extrusion molding, injection-blow molding, rotational molding or compression molding

[Effect of the invention]

The present invention provides a method for producing a highly polymerized aromatic polycarbonate resin by a simple process in which an aromatic polycarbonate with terminally occupied ends undergoes a transesterification reaction with an aliphatic diol compound which is a compound having specific active hydrogen atoms in the presence of a reduced pressure transesterification catalyst, which allows to obtain a high molecular weight polymer having good quality by melt polymerization under moderate conditions in a short time. With respect to the aromatic polycarbonate subjected to the transesterification reaction (or a chain extension reaction or a highly polymerizing reaction), an aromatic polycarbonate resin obtained by conventional interfacial polymerization or an aromatic polycarbonate resin obtained by melt polymerization can be used. An aromatic polycarbonate used once polymerized and subjected to a molding process can also be used.

According to the present invention as mentioned above, the time required to highly polymerize the polycarbonate can be shortened and the process can be carried out under moderate conditions such as a low temperature and a high reaction rate of highly polymerizing, which allows to avoid conditions High temperature and high shear compared to conventional methods. Therefore, coloration, crosslinking or gelation do not occur in the polymer, which allows to obtain an aromatic polycarbonate resin excellent in color and quality. In addition, since the aliphatic diol compound itself It is used as a bonding agent, highly polymerization can be achieved by a simpler process in which the process of reacting it with a salicylic acid derivative is not required compared to the conventional method of using a bonding agent such as a derivative of Salicylic acid, and therefore the present method is economically effective.

Although the highly polymerized aromatic polycarbonate resin obtained by the process of the present invention is a polycarbonate copolymer containing an aliphatic diol compound as a structural unit, it has comparable properties compared to the conventional polycarbonate homopolymer such as bisphenol. A, and what is more, it is highly polymerized by melt polymerization without difficulty.

While interfacial polymerization using phosgene or other organic solvents is avoided due to environmental problems, the present molten polymerization method allows to obtain a polycarbonate having comparable properties compared to highly polymerized polycarbonate such as bisphenol A obtained by polymerization interfacial, which is quite significant.

Mode (s) for carrying out the invention

The process for producing a highly polymerized aromatic polycarbonate resin comprises a highly polymerizing process in which the aromatic polycarbonate is bonded with an aliphatic diol compound through a transesterification reaction in the presence of a reduced pressure transesterification catalyst to increase the molecular weight.

(1) Aromatic polycarbonate

The aromatic polycarbonate to be highly polymerized in the process of the present invention which is, in other words, a polycarbonate resin before the transesterification reaction in the highly polymerizing process of the present invention, hereinafter "reaction highly polymerizing ”is a polycondensation polymer having the structure represented by the following general formula (1) as a repeating unit.

[Chemical formula 4]

In the above general formula (1), R1 and R2 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1-20 carbon atoms, an alkoxy group having 1-20 atoms of carbon, a cycloalkyl group having 6-20 carbon atoms, an aryl group having 6-20 carbon atoms, a cycloalkoxyl group having 6-20 carbon atoms or an aryloxy group having 6-20 carbon atoms. "P" and "q" each independently represent an integer from 0-4. X represents an organic group selected from the group consisting of divalent organic groups represented by the following general formula (1 '):

[Chemical formula 5]

In the above general formula (1 '), R3 and R4 each independently represent a hydrogen atom, an alkyl group having 1-10 carbon atoms or an aryl group having 6-10 carbon atoms. R3 and R4 can join together to form an aliphatic ring.

The aromatic polycarbonate mentioned above before the highly polymerizing reaction can be synthesized by interfacial polymerization or by melt polymerization. It can also be synthesized by solid phase polymerization or thin layer polymerization. It can also be a recycled polycarbonate coated with used products such as used disc molded products. These polycarbonates can be mixed together to be used as the polymer before the highly polymerizing reaction. For example, a polycarbonate resin obtained by interfacial polymerization can be mixed with a polycarbonate resin obtained by melt polymerization. Or a polycarbonate resin obtained by melt polymerization or interfacial polymerization can be mixed with a recycled polycarbonate coated with, for example, molded product of used discs.

The aromatic polycarbonate prior to the highly polymerizing reaction of the present invention can also be described as a polycondensation product having a reaction product unit of an aromatic dihydroxy compound with a carbonate bond forming compound as the main repeat unit. Therefore, the aromatic polycarbonate prior to the highly polymerizable reaction can be easily obtained by a known transesterification method in which an aromatic dihydroxy compound is derived which derives the corresponding structure with a diester carbonate in the presence of a basic catalyst, or by a known interfacial polymerization method in which an aromatic dihydroxy compound is reacted, for example, with phosgene in the presence of an acid binding agent.

Examples of the aromatic dihydroxy compounds to be used include a compound represented by the following general formula (2):

In the above general formula (2), R1 and R2 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1-20 carbon atoms, an alkoxy group having 1-20 atoms of carbon, a cycloalkyl group having 6-20 carbon atoms, an aryl group having 6-20 carbon atoms, a cycloalkoxyl group having 6-20 carbon atoms or an aryloxy group having 6-20 carbon atoms. "P" and "q" each independently represent an integer from 0-4. X represents an organic group selected from the group consisting of divalent organic groups represented by the following general formulas (2 '):

[Chemical formula 7]

R 3

r 4

In the above general formula (2 '), R3 and R4 each independently represent a hydrogen atom, an alkyl group having 1-10 carbon atoms or an aryl group having 6-10 carbon atoms. R3 and R4 can join together to form an aliphatic ring.

Examples of aromatic dihydroxy compounds include

bis (4-hydroxyphenyl) methane,

1.1 -bis (4-hydroxyphenyl) ethane,

2.2- bis (4-hydroxyphenyl) propane,

2.2- bis (4-hydroxyphenyl) butane,

2.2- bis (4-hydroxyphenyl) octane,

bis (4-hydroxyphenyl) phenylmethane,

1.1 -bis (4-hydroxyphenyl) -1-phenylethane,

bis (4-hydroxyphenyl) diphenylmethane,

2.2- bis (4-hydroxy-3-methylphenyl) propane,

1.1-bis (4-hydroxy-3-tert-butylphenyl) propane,

2.2- bis (3,5-dimethyl-4-hydroxyphenyl) propane,

2.2- bis (4-hydroxy-3-phenylphenyl) propane,

2.2- bis (3-cyclohexyl-4-hydroxyphenyl) propane,

2.2-bis (4-hydroxy = 3 = bromophenyl) propane,

2.2- bis (3,5-dibromo-4-hydroxyphenyl) propane,

1.1 -bis (4-hydroxyphenyl) cyclopentane,

1.1-bis (4-hydroxyphenyl) cyclohexane,

2.2- bis (4-hydroxy-3-methoxyphenyl) propane,

4,4'-dihydroxydiphenyl ether,

4,4'-dihydroxy-3,3'-dimethylphenyl ether,

4,4'-dihydroxyphenyl sulfide,

4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide,

4,4'-dihydroxydiphenylsulfoxide,

4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide,

4,4'-dihydroxydiphenylsulfone and

4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone.

Among them, it is preferable to use 2,2-bis (4-hydroxyphenyl) propane for the reason that that stable as a monomer, that the one with a low impurity content is readily available and so on.

The aromatic polycarbonate resin of the present invention can be obtained by combining two or more of the various monomers mentioned above (aromatic dihydroxy compounds) if necessary for the purpose of controlling optical properties such as controlling a glass transition temperature, improving fluidity , improve the refractive index and reduce birefringence.

The basic method of the process for producing the aromatic polycarbonate before the highly polymerizing reaction will be described below.

In interfacial polymerization, examples of carbonate bond forming compounds include carbonyl halides such as phosgene and haloformates.

In the case of using phosgene as a carbonate bond forming compound, the reaction is usually carried out in the presence of an acid binding agent and a solvent. Examples of binding agents of acid include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amines such as pyridine. Examples of solvents include halogenated hydrocarbons such as methylene chloride and chlorobenzene. In addition, a catalyst such as tertiary amines or quaternary ammonium salts can be used to accelerate the reaction. The reaction temperature is usually in the range from 0 ° C to 40 ° C and the reaction time is usually in the range from several minutes to 5 hours.

In the case of polymerization in the molten state, diester carbonate is used as the carbonate bond forming compound. Examples of carbonate diesters include a compound represented by the following general formula (4):

[Chemical formula 8]

or

A ------ OR ------ C ------ OR ------ A (4)

In the above general formula (4), "A" represents a monovalent, branched or linear hydrocarbon group having 1-10 carbon atoms that can be substituted. The two "A" can be the same or different from each other. Examples of the diester carbonate include aromatic diester carbonates such as diphenyl carbonate, ditolyl carbonate, bis (2-chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate and bis (4-phenylphenyl carbonate). If necessary, other diester carbonates such as dimethyl carbonate, diethyl carbonate, dibutyl carbonate and dicyclohexyl carbonate can be used. Among them, it is preferable to use diphenyl carbonate from the point of view of reactivity, the stability against the coloration of the resin thus obtained and the cost. It is preferable to use diester carbonate in an amount of 0.95-1.30 moles, more preferably in an amount of 0.98-1.20 moles, per mole of the total amount of the aromatic dihydroxy compound.

The melt polymerization using diester carbonate as the carbonate bond forming compound is carried out by stirring the aromatic dihydroxy component with diester carbonate at a predetermined rate in heating under an inert gas atmosphere and then distilling off the alcohols or Phenols produced.

While the reaction temperature depends on the boiling point of the alcohol or phenol thus produced, it is usually in the range from 120 ° C to 350 ° C. The reaction is carried out under reduced pressure from the beginning and is completed by continuously distilling the alcohols or phenols produced. Basic compounds or transesterification catalysts that are commonly used to accelerate the reaction can be used. The aromatic polycarbonate before the highly polymerizing reaction in the present invention is preferably obtained by the transesterification reaction between an aromatic dihydroxy compound and a diester carbonate. The aromatic polycarbonate prior to the highly polymerizing reaction in the present invention is more preferably a prepolymer with terminally occupied ends obtained by the reaction between an aromatic dihydroxy compound and a diester carbonate.

With respect to the terminal groups of the aromatic polycarbonate with ends occupied in a terminal manner mentioned above, the content of terminal groups with occupied ends derived from an aromatic monohydroxyl compound based on the total amount of the terminal groups is preferably 60 mol% or more, more preferably 70% or more, most preferably 80% or more. In this case, the specific effect of the present invention can be shown remarkably.

The content of terminal groups with busy ends based on the total amount of the terminal groups of a polymer can be analyzed by 1 H-NMR analysis of the polymer. It is also possible to analyze by measuring the concentration of terminal hydroxyl groups by spectrometric measurements using Ti complex. The concentration of terminal hydroxyl groups by this measurement is preferably 1,500 ppm or less, more preferably 1,000 ppm or less. In this case, the effect of the highly polymerizing reaction is enhanced which will result in a preferred result.

The binding reaction (or the highly polymerizing reaction) in the highly polymerizing process of the present invention is to use the transesterification reaction between the end groups with busy ends and the introduced aliphatic diol compound. Therefore, when the content of the terminal hydroxyl groups is greater than the range mentioned above or the content of terminal groups with busy ends is smaller that the range mentioned above, the effect of the increase in molecular weight may not be sufficiently achieved by the binding reaction (the highly polymerizing reaction).

Examples of terminal groups with busy ends include a phenyl terminal group, a cresyl terminal group, an o-tolyl terminal group, a p-tolyl terminal group, a pf-butylphenyl terminal group, a biphenyl terminal group, a terminal group or -methoxycarbonylphenyl and a p-cumylphenyl terminal group.

Among them, a terminal group derived from an aromatic monohydroxyl compound having a low boiling point that can be easily removed from the reaction system of the binding reaction described below is preferable. A phenyl terminal group or a p-ferc-butylphenyl terminal group is more preferable.

In the case of interfacial polymerization, the terminal group with busy ends can be introduced using a terminal group terminating agent at the time of producing the aromatic polycarbonate. Examples of the terminal group terminating agents include p-ferc-butyl phenol, phenol, p-cumylphenol and long chain alkyl substituted phenol. The amount of the terminal group terminating agent can be determined correctly according to the expected content of aromatic polycarbonate terminal groups which means the desired molecular weight of the aromatic polycarbonate, the reaction apparatus to be used or the reaction conditions.

In the case of polymerization in the molten state, the terminal groups with busy ends can be introduced using diester carbonate such as diphenyl carbonate in an amount in excess of that of the aromatic dihydroxy compound at the time of producing the aromatic polycarbonate. Although it depends on the reaction apparatus to be used and the reaction conditions, diester carbonate is preferably used in an amount of 1.00 to 1.30 moles, more preferably 1.02 to 1.20 moles per mole of the aromatic dihydroxy compound, whereby an aromatic polycarbonate which satisfies the content of end groups with occupied ends mentioned above can be obtained.

According to the present invention, it is preferable to use a prepolymer with terminally occupied ends obtained by the transesterification reaction between an aromatic dihydroxyl compound and a diester carbonate such as aromatic polycarbonate before the highly polymerizing reaction.

In addition, at the time of producing the aromatic polycarbonate having the repeating units represented by the general formula (1) mentioned above, a dicarboxylic acid compound may be used together with the aforementioned aromatic dihydroxy compound to produce polyester carbonate.

Examples of preferable dicarboxylic acid compounds include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. In addition, these dicarboxylic acid compounds may preferably be reacted in the form of an acid chloride or an ester compound. In addition, at the time of producing a polyester carbonate resin, dicarboxylic acid is preferably used in an amount of 0.5 to 45 mol%, more preferably 1 to 40 mol%, based on 100 mol% of the total amount of the hydroxyl component mentioned above and the dicarboxylic acid component. Regarding the molecular weight of the aromatic polycarbonate before the highly polymerizing reaction to be used in the highly polymerizing process of the present invention, it is preferable that the weight average molecular weight (MW) of the prepolymer is in the range of 5,000 to 60,000, more preferably in the range from 10,000 to 50,000, most preferably in the range from 10,000 to 40,000.

When a prepolymer having a low molecular weight outside the previous range is used, the influence of the copolymerization on the properties of the polymer could be severe. Although it could allow the modification of the properties of the polymer, it would not be preferable in terms of the effect of high polymerization of the aromatic polycarbonate.

When a prepolymer having a greater molecular weight outside the previous range is used, the concentration of the active terminal groups could be decreased, which could cause insufficient effect of the high polymerization effect. In addition, since the prepolymer is a high viscosity polymer, it is necessary to carry out the reaction under conditions of high temperature, high shear and long term, which is not preferable to obtain a high quality aromatic polycarbonate resin.

(2) Aliphatic diol compound

According to the present invention, the aromatic polycarbonate with terminally occupied ends mentioned above is reacted with an aliphatic diol compound as a binding agent in the presence of a transesterification catalyst under reduced pressure, whereby high polymerization can be achieved in a manner Fast in moderate conditions. That is, the terminal group with busy ends derived from the aromatic hydroxyl compound present in the polycarbonate before the highly polymerizing reaction is replaced by a alcoholic hydroxyl group, thus promoting the binding reaction between the aromatic polycarbonate molecules before the highly polymerizing reaction to increase the molecular weight of the resulting molecule.

The aliphatic diol compound to be used in the highly polymerizing process of the present invention requires a boiling point greater than that of the aromatic monohydroxyl compound that is produced accompanied by the high polymerization reaction from the aromatic polycarbonate with busy ends. in a terminal manner subjected to the highly polymerizing reaction and which is removed by distillation. Furthermore, since it has to be immobilized at the temperature and pressure mentioned above, it is preferable to use an aliphatic diol compound having a relatively higher boiling point for the binding reaction of the present invention. More precisely, an aliphatic diol compound having a boiling point of 240 ° C or higher, preferably 250 ° C or higher, is used. Although the upper boiling point limit should not be particularly limited, it would be sufficient to have a boiling point of 500 ° C or less.

The term "aliphatic diol compound" means a compound having a cyclic or chain aliphatic hydrocarbon group such as an alkylene group or a cycloalkylene group attached to the terminal hydroxyl (-OH) groups.

According to the present invention, the aliphatic diol compounds are 4,4'-bis (2-hydroxyethoxy) biphenyl, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, fluorenoglycol and fluorenedioethanol.

Each can be used independently or two or more of them can be used in combination with each other.

With respect to the aliphatic diol compound actually used, the species of the available compounds can be varied depending on the reaction conditions.

The practical reaction scheme of binding and highly polymerizing reaction by the aliphatic diol compound is exemplified as follows:

[Chemical formula 13]

In the above reaction scheme, the aromatic monohydroxyl compounds represented by "R-OH" are removed as the reaction proceeds under reduced pressure. Therefore, the molecular weight of the polymer can be increased.

The amount of the aliphatic diol compound to be used according to the present invention is preferably 0.01 to 1.0 moles, more preferably 0.1 to 1.0 moles, even more preferably 0.1 to 0.5 moles, most preferably 0.2 to 0.4 moles, per mole of the total amount of the end groups of the aromatic polycarbonate before the highly polymerizing reaction.

When the amount of the aliphatic diol compound to be used is too large beyond the above range, the insertion reaction in which the aliphatic diol compound is inserted into the main chain of the aromatic polycarbonate resin as a component could occur. of copolymerization, which could cause a serious influence of the copolymerization on the properties of the polymer due to the increase in the ratio of copolymerization. Although it could allow the modification of the polymer properties, it would not be preferable as to the effect of the high polymerization of the aromatic polycarbonate.

When the amount of the aliphatic diol compound to be used is too small beyond the above range, high polymerization could be ineffective, which would not be preferable.

In the present invention, "the total amount of the polycarbonate end groups" or "the total amount of the polymer end groups" can be determined by calculating as follows: in the case of unbranched polycarbonate or straight chain polymer, for example , the number of terminal groups per molecule is two. By Therefore, when the amount of polycarbonate without branches is 0.5 moles, the total amount of the terminal groups will be 1 mole.

In the case of polycarbonate having branches, the terminal groups of the branched chain are also included in the total amount of the terminal groups. The total amount of the terminal groups that include the branched chain end groups can be determined by NMR analysis or by calculating it from molecular weight and / or an introductory amount of branching agents.

It is desirable that the content of impurities such as chlorine, nitrogen, alkali metals and heavy metals in the aliphatic diol compound be low. Examples of alkali metals include sodium, potassium and salts or derivatives thereof. Examples of heavy metals include iron, nickel and chromium.

Regarding the content of these impurities, the chlorine content is preferably 1000 ppm or less, the nitrogen content is preferably 100 ppm or less and the alkali metal content is preferably 10 ppm or less. With respect to heavy metals, the iron content is preferably 3 ppm or less, the nickel content is preferably 2 ppm or less and the chromium content is preferably 1 ppm or less.

(3) Highly polymerizing reaction

The highly polymerizing reaction in the highly polymerizing process of the present invention is a transesterification reaction. As the catalyst to be used for the transesterification reaction which is the highly polymerizing reaction of the present invention, a basic compound catalyst and a transesterification catalyst commonly used as a catalyst to produce polycarbonate can be used.

Examples of the basic compound catalysts include alkali metal compounds and / or alkaline earth metal compounds and nitrogen containing compounds.

Preferable examples of alkali metal compounds and / or alkaline earth metal compounds include salts of organic acid, inorganic salts, oxide, hydroxide, hydride, alkoxide, quaternary ammonium hydroxide and salts thereof and alkali metal and alkaline earth metal amines. These compounds can each be used independently or two or more of them can be used in combination with each other.

Examples of alkali metal compounds include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, acetate potassium, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium phenylborate, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenyl phosphate, a disodium salt of bisphenol A, a dipotassium salt of bisphenol A, a dicesio salt of bisphenol A and a dilithium salt of bisphenol A, a salt of sodium phenol, a potassium salt of phenol, a cesium salt of phenol, a lithium salt of phenol.

Examples of alkaline earth metal compounds include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydrogen carbonate, calcium hydrogen carbonate, strontium hydrogen carbonate, barium hydrogen carbonate, magnesium carbonate, calcium carbonate, carbonate Strontium, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate and magnesium phenyl phosphate.

Examples of nitrogen-containing compounds include bases such as quaternary ammonium hydroxides containing alkyl groups and / or aryl groups such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and trimethylbenzylammonium hydroxide; tertiary amines such as triethylamine, dimethylbenzylamine and triphenylamine; secondary amines such as diethylamine and dibutylamine; primary amines such as propylamine and butylamine; imidazoles such as 2-methylimidazole, 2-phenylimidazole and benzoimidazole; and a base or a basic salt such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate and tetraphenylammonium tetraphenylborate, or basic salts thereof.

With respect to the transesterification catalyst, zinc, tin, zirconium or lead salts can preferably be used. Each can be used independently or two or more of them can be used in combination with each other. Examples of the transesterification catalysts include zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin (II) chloride, tin (IV) chloride, tin (II) acetate, tin (IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead acetate (II) and lead acetate (IV).

The above catalysts can be used in an amount preferably 1x10-9 to 1x10-3 moles, more preferably 1x10-7 to 1x10-5 moles per mole of the total amount of dihydroxyl compounds.

The reaction temperature of the highly polymerizing reaction or the binding reaction (or the connection reaction) by the aforementioned aliphatic diol compound is preferably in the range from 240 ° C to 320 ° C, more preferably in the range from 260 ° C to 310 ° C, most preferably in the range from 270 ° C to 300 ° C.

The degree of pressure reduction is preferably in the range of 13 kPaA (100 torr) or less, more preferably in the range of 1.3 kPaA (10 torr) or less, even more preferably in the range from 0.67 kPaA to 0.013 kPaA (from 5 torr to 0.1 torr). When the highly polymerizing reaction is carried out at normal pressure, degradation of the molecular weight of the polymer could be induced.

By using the aliphatic diol compound, the increase in weight average molecular weight (MW) of the aromatic polycarbonate resin after the highly polymerizing reaction can preferably be increased by 5,000 or more, more preferably 10,000 or more, even more preferably at 15,000 or more compared to that of aromatic polycarbonate before the highly polymerizing reaction.

The weight average molecular weight (MW) of the highly polymerized aromatic polycarbonate resin obtained by the process of the present invention is 30,000 to 100,000, preferably 30,000 to 80,000.

The type of reaction apparatus or the materials of the containers are not particularly limited and any of the known apparatus can be used. Any of the continuous polymerization or discontinuous polymerization can be used. The reaction apparatus used to carry out the aforementioned reaction may be a vertical reactor equipped with an anchor blade, a Maxblend impeller or a helical belt blade, or it may be a horizontal reactor equipped with a vane blade, a blade reticular structure or a lens-shaped blade, or it can be an extruder equipped with a spindle. Furthermore, it is desirable to use a reaction apparatus in which the aforementioned apparatus are correctly combined with each other taking into account the viscosity of the polymer. It is more desirable to use a reaction apparatus equipped with a spindle that has good horizontal agitation efficiency and a unit capable of dealing with reduced pressure.

It is even more desirable to use a biaxial extruder or a horizontal reactor that has a polymer seal and a vent.

With respect to the material of the apparatus, it is desirable to use a material that has no influence on the color tone of the polymer such as stainless steel selected from SUS310, SUS316 or SUS304, nickel and iron nitride. In addition, polishing processing, electropolishing processing and / or metallizing such as chrome plating can be applied to the internal side of the apparatus which is a place in contact with the polymer.

According to the present invention, a catalyst deactivator can be added to the highly polymerized polymer in the highly polymerizing process mentioned above. In general, it is desirable to employ a method of adding known acidic materials to deactivate the catalyst. Examples of the acidic materials include aromatic sulfonic acid such as p-toluenesulfonic acid, aromatic sulfonic acid esters such as butyl p- toluenesulfonate, organohalides such as stearic acid chloride, butyric acid chloride, benzoyl chloride and acid chloride toluenesulfonic, alkyl sulfate such as dimethyl sulfate and organic halides such as benzyl chloride.

After deactivating the catalyst, a process in which to remove the low boiling compounds in the polymer by degassing under reduced pressure ranging from 0.013 to 0.13 kPaA (from 0.1 torr to 1 torr) at a temperature ranging from 200 ° C to 350 ° C. For this procedure, a horizontal reactor equipped with an agitator blade with excellent surface renewal capacity such as a vane blade, a reticular structure blade and a lens-shaped blade or a thin film evaporator can preferably be used.

According to the present invention, various additives such as thermal stabilizer, antioxidant, pigment, dye enhancing agents, fillers, ultraviolet absorbers, lubricant, mold release agents, crystal nucleating agents, plasticizers, improving agents can be added to the polymer. fluency and antistatic agents.

These additives can be mixed with the polycarbonate resin by a conventional method. For example, a method can be used correctly in which the components are subjected to a dispersion mixture by a fast mixer such as a drum mixer, a Henschel mixer, a belt mixer and a supermixer, and then the mixture is it is melted and kneaded by, for example, an extruder, a Banbury mixer or a roller mixer.

The polycarbonate disclosed in the present invention can be used for various molded products or sheet or film products obtained by injection molding, blow molding, extrusion molding, injection-blow molding, rotational molding or compression molding. In the case of using polycarbonate for these purposes, the polycarbonate produced by the process of the present invention can be used independently, or it can be used by mixing it with other polymers. Depending on the intended use, it can also be used accompanied by a hard or laminated coating procedure.

Examples of molded products include optical media products such as compact discs, digital video discs, mini-discs and magnetic optical discs, optical communication media such as optical fibers, optical components such as a car's headlight lens and a a camera lens, optical equipment components such as a siren light cover and a lighting lamp cover, replacement items for the window glass of a vehicle such as a train and a car, replacement items for the glass of a house window, smart window components such as a sunroof and a greenhouse roof, glasses or glasses frames, sunglasses and glasses, packages or frames of office automation equipment such as a photocopier , a fax machine and a personal computer, household appliances such as a television and a microwave oven, make up electronic devices such as a connector and an IC tray, protective equipment such as a helmet, a protector and a protective mask, dishes such as a tray and medical items such as a dialysis case and artificial dentures.

Examples

The present invention will be described in more detail below, referring to examples.

The data in the examples below were measured using the following methods and / or devices:

1) Weight average molecular weight in terms of polystyrene (PM): measured by GPC using tetrahydrofuran as a developing solvent, an analytical curve was prepared using a standard polystyrene having a known molecular weight (molecular weight distribution = 1). Based on the analytical curve, the PM was calculated from the retention time of CPG.

2) Glass transition temperature (Tg): measured by differential scanning calorimetry (DSC).

3) Total amount of polymer terminal groups: 0.25 g of a polymer sample was dissolved in 5 ml of deuterated chloroform and then the amount of the terminal groups was measured at 23 ° C using a 1H-NMR magnetic resonance spectrometer nuclear, trade name "LA-500", manufactured by JASCO Corporation. The result was shown as the number of moles per tonne of polymer.

4) Concentration of terminal hydroxyl groups (ppm): measured by UV / visible spectroscopy (546 nm) of a complex formed from the polymer and titanium tetrachloride in a methylene chloride solution.

5) Polymer color (YI value): 4 g of a polymer sample was dissolved in 25 ml of methylene chloride and then the YI value was measured using a spectroscopy colorimeter manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD, trade name "SE-2000".

<Example 1-2>

The aromatic polycarbonate was prepared from bisphenol A and diphenyl carbonate by melt polymerization using 1.1 moles of diphenyl carbonate per mole of bisphenol A in the presence of sodium hydrogen carbonate (NaHCO3) as catalyst.

More precisely, 10.00 kg (43.8 moles) of 2,2-bis (4-hydroxyphenyl) propane, 10.56 kg (49.3 moles) of diphenyl carbonate and 1 ^ mol / mol of hydrogen carbonate were loaded of sodium as a catalyst in a 50-liter SUS316 reactor equipped with a stirrer and distillation assembly, a medium heat heating unit, and the temperature was raised to 180 ° C in a nitrogen atmosphere. After melting, they were stirred for 30 minutes.

Subsequently, the pressure was reduced to 20 kPaA (150 torr), and at the same time, the temperature was raised to 200 ° C at a speed of 60 ° C / h. Maintaining the temperature for 40 minutes, the transesterification reaction was carried out.

Then, the temperature was raised to 225 ° C at a rate of 75 ° C / h, and the temperature was maintained for 15 minutes. Subsequently, the temperature was raised to 260 ° C at a rate of 65 ° C / h, and the pressure was reduced to 0.13 kPaA (1 torr) or less, requiring 1 hour to obtain 10 kg of granulated aromatic polycarbonate prepolymer which It has the weight average molecular weight (MW) of 31,000, the total number of terminal groups of 256 moles and the concentration of terminal hydroxyl groups of 400 ppm.

200 g of the granulated aromatic polycarbonate prepolymer thus obtained and the aliphatic diol compound, whose name and the amount used are shown in Table 1, were loaded in a 1000 ml SUS316 kneader mounted with an oil heating jacket. With respect to the catalyst for the highly polymerizing reaction, the polymerization catalyst (NaHCO3) which had been used in the process of preparing the aromatic polycarbonate before bonding was used directly.

The mixture was stirred and kneaded for 30 minutes at a jacket temperature of 290 ° C under reduced pressure of 0.04 kPaA (0.3 torr). Distilled phenol from the reaction system was condensed in a cooling tube to remove it. The aromatic polycarbonate thus obtained was extracted to measure the weight average molecular weight. The properties of the polymer thus obtained were shown in Table 1.

<Examples 3-7>

In the same manner as in Example 1, the preparation of aromatic polycarbonate from bisphenol A and diphenyl carbonate was carried out by melt polymerization using 1.1 moles of diphenyl carbonate per mole of bisphenol A by polymerization in molten state in the presence of 1 mol / mol sodium hydrogen carbonate (NaHCO3) as a catalyst to obtain granulated aromatic polycarbonate prepolymer having the weight average molecular weight (MW) of 31,000, the total number of terminal groups of 256 moles and the concentration of terminal hydroxyl groups of 400 ppm.

30 g of the granulated aromatic polycarbonate prepolymer thus obtained was loaded into a 300 cc four-mouth flask equipped with a stirrer and a distiller mounted with an oil bath. The polymerization catalyst (NaHCO3) which had been used in the process of preparing the aromatic polycarbonate before bonding as a catalyst during the highly polymerizing reaction was used directly.

Heating and melting were carried out at an oil bath temperature of 290 ° C under vacuum. Subsequently, the aliphatic diol compound whose name and the amount used were shown in Table 1 was charged thereto and kneaded with stirring for 30 minutes at an oil bath temperature of 290 ° C under reduced pressure of 0.04 kPaA (0.3 torr). Distilled phenol from the reaction system was condensed in a cooling tube to remove it. The aromatic polycarbonate thus obtained was extracted to measure the weight average molecular weight. The properties of the polymer thus obtained were shown in Table 1.

<Examples 8-9>

The preparation of aromatic polycarbonate was prepared from bisphenol A and phosgene by interfacial polymerization using p-ferc-butylphenol as the terminal group terminating agent to obtain flakes of aromatic polycarbonate prepolymer having the weight average molecular weight (MW) of 32,000, the total number of terminal groups of 253 moles and the concentration of terminal hydroxyl groups of 200 ppm.

200 g of flakes of the aromatic polycarbonate prepolymer thus obtained, the aliphatic diol compound whose name and the amount used were shown in Table 1 and 1 pmol / mol of catalyst (NaHCO3) were loaded in a 1000 ml SUS316 mixer mounted with An oil heating jacket. The amount of catalyst was calculated as the number of moles based on the amount of bisphenol A units.

Kneading was carried out with stirring for 30 minutes at an oil bath temperature of 290 ° C under reduced pressure of 0.04 kPaA (0.3 torr). Distilled p-ferc-butylphenol was condensed from the reaction system in a cooling tube to remove it. The aromatic polycarbonate thus obtained was extracted to measure the weight average molecular weight. The properties of the polymer thus obtained were shown in Table 1.

<Comparative example 1>

45.6 g (0.20 mol) of 2,2-bis (4-hydroxyphenyl) propane, 23.3 g (0.202 mol) of diphenyl carbonate and 1 pmol / mol of sodium hydrogen carbonate as catalyst were charged, which It was calculated as the number of moles based on the amount of bisphenol A units in a four-neck 300 cc flask equipped with a stirrer and a distiller. Stirring was carried out for 30 minutes by heating at 180 ° C in a nitrogen atmosphere. Subsequently, the pressure was reduced to 20 kPaA (150 torr), and at the same time, the temperature was raised to 200 ° C at a speed of 60 ° C / h. Maintaining the temperature for 40 minutes, the transesterification reaction was carried out.

Then, the temperature was raised to 225 ° C at a rate of 75 ° C / h and the temperature was maintained for 10 minutes. Subsequently, the temperature was raised to 290 ° C at a rate of 65 ° C / h and the pressure was reduced to 0.13 kPaA (1 torr) or less, requiring 1 hour. The polymerization was carried out by reacting with stirring for 6 hours in total. In the last half of the polymerization, it became difficult to remove the phenol due to the increase in viscosity, which caused the rate of increase in molecular weight to be too slow.

6 hours were required to increase the molecular weight to a comparable level, which was so long that the polymer was colored significantly. The properties of the polymer thus obtained were shown in table 2.

<Comparative Example 2>

The experiment was carried out in the same manner as Example 1 except that the use of aliphatic diol compounds was avoided. The properties of the polymer thus obtained were shown in table 2.

<Comparative example 3>

The experiment was carried out in the same manner as Example 1 except that the highly polymerizing process was produced at normal pressure. The properties of the polymer thus obtained were shown in Table 2. <Comparative Example 4>

The experiment was carried out in the same manner as Example 8 except that the use of diol compounds was avoided. The properties of the polymer thus obtained were shown in table 2.

<Comparative example 5>

The experiment was carried out in the same manner as Example 8 except that the highly polymerizing process was produced at normal pressure. The properties of the polymer thus obtained were shown in Table 2. <Comparative Example 6>

The experiment was carried out in the same manner as Example 1 except that 2,2-bis (4-hydroxyphenyl) propane was used which was an aromatic diol compound having a boiling point of 420 ° C, then in this document "BPA", as a diol compound. The properties of the polymer thus obtained were shown in table 2.

<Comparative Example 7>

The experiment was carried out in the same manner as Example 8 except that BPA, which was an aromatic diol compound, was used as the diol compound. The properties of the polymer thus obtained were shown in table 2.

<Comparative Example 8>

The experiment was carried out in the same manner as Example 1 except that 1.1 g of 1,4-skethanol was used which was a low boiling aliphatic diol having a boiling point of 228 ° C, at hereinafter "BD", as a diol compound. The properties of the polymer thus obtained were shown in table 2.

<Comparative Example 9>

The experiment was carried out in the same manner as Example 1 except that 1.3 g of neopentyl glycol was used which was a low boiling aliphatic diol having a boiling point of 211 ° C, hereinafter "NPG" document, as a diol compound. The properties of the polymer thus obtained were shown in table 2.

<Comparative example 10>

The experiment was carried out in the same manner as Example 8 except that 1.3 g of NPG was used as a diol compound. The properties of the polymer thus obtained were shown in table 2.

<Examples 10-11>

The experiment was carried out in the same manner as Example 1 except that the compounds whose name and the amount used were shown in Table 3 as a diol compound were used. The properties of the polymer thus obtained were shown in table 3.

<Examples 12-13>

The experiment was carried out in the same manner as Example 3 except that the compounds whose name and the amount used were shown in Table 3 as a diol compound were used. The properties of the polymer thus obtained were shown in table 3.

The diol compounds used above were as follows:

BPEF: 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene having a boiling point of approximately 625 ° C BP-2EO: 4,4'-bis (2-hydroxyethoxy) biphenyl having a point of boiling of about 430 ° C BPA-2EO: 2,2'-bis [(2-hydroxyethoxy) phenyl] propane having a boiling point of about 480 ° C FG: fluorenoglycol having a boiling point of about 370 ° C

PCPDM: penta-cyclopentadecanedimethanol having a boiling point of approximately 420 ° C CHDM: cyclohexan-1,4-dimetanol having a boiling point of approximately 280 ° C

DDM: decalin-2,6-dimetanol having a boiling point of approximately 341 ° C

BD: 1,4-butanediol having a boiling point of 228 ° C

NPG: neopentyl glycol having a boiling point of 211 ° C

FE: Fluorenedioethanol having a boiling point of approximately 410 ° C

[Table 3]

* 1) Same as in tables 1 and 2.

** Reference example, not according to the claimed invention.

FE: Fluorenedioethanol having a boiling point of approximately 410 ° C

As shown in the previous examples, the polycarbonate resins obtained by the process of the present invention were excellent in color, having a low YI value. In addition, their Tg values were comparable with those of the BPA homopolymer having the same level of molecular weight. This means that, using the process of the present invention, a polycarbonate resin having comparable properties to the highly polymerized BPA homopolymer that had been difficult to manufacture by conventional melt polymerization in a simple manner by polymerization can be obtained molten state that is an excellent method in terms of safety and environmental aspects.

Industrial applicability

According to the present invention, a process for producing highly polymerized aromatic polycarbonate can be provided under moderate conditions for a short processing time.

Claims (14)

1. Process for producing a highly polymerized aromatic polycarbonate resin comprising a highly polymerizing process, wherein the aromatic polycarbonate is bonded with an aliphatic diol compound having a boiling point of 240 ° C or higher through a reaction of transesterification in the presence of a transesterification catalyst under reduced pressure to increase molecular weight, wherein the aliphatic diol compound is selected from the group consisting of 4,4'-bis (2-hydroxyethoxy) biphenyl, 9,9'-bis [4- (2-hydroxyethoxy) phenyl] fluorene, fluorenoglycol and fluorenedioethanol, Y wherein the highly polymerized aromatic polycarbonate resin has a weight average molecular weight (MW) of 30,000-100,000. 2. A process according to claim 1, wherein said aliphatic diol compound is added in the amount of 0.01 to 1.0 mol per mole of the total amount of the end groups of the aromatic polycarbonate before said transesterification reaction. 3. The method according to claim 1 or 2, wherein the aromatic polycarbonate prior to said transesterification reaction in the highly polymerizing process has at least partially occupied ends. 4. The method of claim 3, wherein the aromatic polycarbonate prior to said transesterification reaction is a prepolymer with terminally occupied ends obtained by reacting an aromatic dihydroxy compound with diester carbonate. 5. A process according to claim 3 or 4, wherein the aromatic polycarbonate prior to said transesterification reaction in the highly polymerizing process has the concentration of terminal hydroxyl groups of 1,500 ppm or less. Method according to any one of claims 1 to 5, wherein the weight average molecular weight (MW) of the highly polymerized aromatic polycarbonate resin after the transesterification reaction in the highly polymerizing process is increased by 5,000 or more. compared to that of aromatic polycarbonate before the transesterification reaction. 7. The method according to any one of claims 1 to 6, wherein the weight average molecular weight (MW) of the aromatic polycarbonate before the transesterification reaction in the highly polymerizing process is 5,000 to 60,000. 8. A method according to any one of claims 1 to 7, wherein the transesterification reaction in the highly polymerizing process is carried out at a temperature ranging from 240 ° C to 320 ° C under reduced pressure. 9. The method according to any one of claims 1 to 8, wherein the transesterification reaction in the highly polymerizing process is carried out at a reduced pressure ranging from 13 kPaA (100 torr) to 0.01 kPaA (0, 01 torr). 10. A method according to any one of claims 1 to 9, comprising a prepolymer production process in which a prepolymer is produced with ends occupied in a terminal manner by reacting an aromatic dihydroxy compound with diester carbonate, and a highly process polymerizer in which said prepolymer with terminally occupied ends binds with an aliphatic diol compound having a boiling point of 240 ° C or higher through a transesterification reaction in the presence of a reduced pressure transesterification catalyst for Increase molecular weight. 11. Highly polymerized aromatic polycarbonate resin obtainable by the process according to any one of claims 1 to 10. 12. Molded product, sheet or film product obtainable from the highly polymerized aromatic polycarbonate resin according to claim 11, by injection molding, blow molding, extrusion molding, injection-blow molding, rotational molding or compression molding . 13. Molded product according to claim 12, wherein the highly polymerized aromatic polycarbonate resin is used independently or mixed with other polymers. 14. Molded product according to claim 12 or 13, wherein the molded product, sheet product or of movie is selected from optical media products such as compact discs, digital video discs, mini discs and magnetic optical discs, optical means of communication such as optical fibers, optical components such as a car headlight lens and a camera lens, optical equipment components such as a siren light cover and a lighting lamp cover, replacement items for the glass of a window of a vehicle such as a train and a car, replacement items for the glass of a window of a house, smart window components such as a sunroof and a greenhouse roof, glasses or glasses frames, sunglasses and glasses, packages or frames of office automation equipment such as a photocopier, a fax machine and a personal computer, appliance frames such as a television and a microwave oven, electronic components such as a connector and an IC tray, protective equipment such as a helmet, a protector and a protective mask, and Dishes such as a tray and medical items such as a case for dialysis and artificial dentures.